WO2016056577A1 - ハニカム触媒 - Google Patents

ハニカム触媒 Download PDF

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Publication number
WO2016056577A1
WO2016056577A1 PCT/JP2015/078445 JP2015078445W WO2016056577A1 WO 2016056577 A1 WO2016056577 A1 WO 2016056577A1 JP 2015078445 W JP2015078445 W JP 2015078445W WO 2016056577 A1 WO2016056577 A1 WO 2016056577A1
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WIPO (PCT)
Prior art keywords
zeolite
honeycomb
honeycomb catalyst
oxide
mass
Prior art date
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PCT/JP2015/078445
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English (en)
French (fr)
Japanese (ja)
Inventor
剛大 梅本
尚紀 女屋
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イビデン株式会社
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=55653186&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2016056577(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by イビデン株式会社 filed Critical イビデン株式会社
Priority to US15/517,515 priority Critical patent/US20170297007A1/en
Priority to CN201580054527.5A priority patent/CN106794458A/zh
Priority to EP15848275.2A priority patent/EP3205400B1/de
Publication of WO2016056577A1 publication Critical patent/WO2016056577A1/ja

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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
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    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Definitions

  • the present invention relates to a honeycomb catalyst for purifying exhaust gas discharged from an internal combustion engine, and more particularly, to a honeycomb catalyst used in SCR for reducing NOx in exhaust gas.
  • an SCR (Selective Catalytic Reduction) system that uses ammonia to reduce NOx to nitrogen and water is known as one of the systems for purifying automobile exhaust gas.
  • a honeycomb unit in which a large number of through-holes through which exhaust gas passes is provided in the longitudinal direction is used as the SCR catalyst carrier.
  • an extruded unit using zeolite as a main raw material is known.
  • SAPO siliconcoaluminophosphate
  • ⁇ -type zeolite ⁇ -type zeolite
  • ZSM-5-type zeolite and the like are used as the zeolite.
  • Patent Documents 1 and 2 disclose a honeycomb structure in which Al 2 O 3 is contained at a predetermined ratio to improve strength.
  • Patent Document 2 discloses that the composition ratio SiO 2 / Al 2 O 3 is less than 15 and is intended to increase heat resistance and durability when used as an SCR catalyst carrier, and particles A zeolite having a CHA structure having a diameter of 1.0 to 8.0 ⁇ m is disclosed.
  • the CHA-structured zeolite has a large linear expansion coefficient of about -5 ⁇ 10 ⁇ 6 , and expansion / contraction due to absorption / dehydration (water absorption displacement). Because of the large size, cracks may occur during production.
  • the present invention has been made in view of the above-described conventional problems, and its object is to reduce the linear expansion coefficient and reduce the amount of water absorption displacement while suppressing the generation of cracks while maintaining high NOx purification performance. It is an object of the present invention to provide a honeycomb catalyst.
  • a honeycomb catalyst including a honeycomb unit in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall therebetween,
  • the honeycomb unit includes at least two kinds of inorganic particles and an inorganic binder,
  • the inorganic particles include a zeolite having a composition ratio SiO 2 / Al 2 O 3 of less than 15 and a CHA structure, and an oxide having a positive linear expansion coefficient other than zeolite,
  • a honeycomb catalyst having a ratio (X: Y) of a volume (X) of the zeolite to a volume (Y) of the oxide of 50:50 to 90:10.
  • the zeolite having a negative linear expansion coefficient is mixed with an oxide having a positive linear expansion coefficient so as to cancel out the linear expansion coefficient.
  • the coefficient can be suppressed within ⁇ 4.0 ⁇ 10 ⁇ 6 . Therefore, cracks can be prevented from occurring when used as a honeycomb catalyst.
  • the zeolite according to the present invention when the composition ratio SiO 2 / Al 2 O 3 exceeds 15, the NOx purification rate decreases. The reason is that when SiO 2 / Al 2 O 3 is high, the amount of Cu that functions as a catalyst that can be supported decreases.
  • honeycomb catalyst according to any one of (1) to (4), wherein the oxide is at least one selected from the group consisting of alumina, titania and zirconia.
  • the oxide is at least one selected from the group consisting of alumina, titania and zirconia.
  • any oxide may be used as long as it has a positive linear expansion coefficient.
  • at least one selected from the group consisting of alumina, titania and zirconia is preferable.
  • the ratio (X: Y) between the volume (X) of the zeolite and the volume (Y) of the oxide is 60:40 to 85:15, or any one of (1) to (5) Honeycomb catalyst.
  • the volume ratio of the zeolite and the oxide is in the above range, it is possible to improve the strength of the honeycomb unit and adjust the pore diameter while maintaining the NOx purification performance.
  • honeycomb catalyst according to any one of (1) to (6), wherein the zeolite contains 150 to 350 g / L with respect to the entire honeycomb unit.
  • the honeycomb is likely to be displaced due to expansion and contraction due to the absorption and dehydration of zeolite.
  • the amount is lower than 150 g / L, the NOx purification performance is lowered. , NOx purification performance can be maintained high.
  • the density of through-holes in a cross section perpendicular to the longitudinal direction of the honeycomb unit is 62 to 186 / cm 2
  • the partition wall thickness of the honeycomb unit is 0.1 to 0.3 mm
  • honeycomb catalyst according to any one of (1) to (8), wherein the honeycomb catalyst has a cylindrical shape with a diameter of 140 to 350 mm and a length of 75 to 310 mm.
  • the honeycomb catalyst of the present invention is suitable for being mounted on an automobile by having a cylindrical shape with the above size.
  • a honeycomb catalyst capable of reducing the coefficient of linear expansion, reducing the amount of water absorption displacement, and suppressing the occurrence of cracks while maintaining high NOx purification performance.
  • a honeycomb catalyst of the present invention is a honeycomb catalyst including a honeycomb unit in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall therebetween, and the honeycomb unit includes at least two kinds of inorganic particles and an inorganic binder.
  • the inorganic particles include a zeolite having a composition ratio SiO 2 / Al 2 O 3 of less than 15 and a CHA structure, and an oxide having a positive coefficient of linear expansion other than zeolite, and the volume (X) of the zeolite The ratio (X: Y) to the volume (Y) of the oxide is 50:50 to 90:10.
  • the inorganic particles include at least two kinds, the two kinds of inorganic particles being a zeolite having a composition ratio SiO 2 / Al 2 O 3 of less than 15 and a CHA structure, and positive lines other than zeolite It is an oxide having an expansion coefficient. Below, each inorganic particle is demonstrated.
  • the zeolite according to the present invention is a zeolite having a CHA structure with a composition ratio SiO 2 / Al 2 O 3 of less than 15 (hereinafter also referred to as “CHA-type zeolite”).
  • the zeolite according to the present invention is a zeolite having a crystal structure equivalent to that of naturally occurring chabasite, which is named and classified by the structure code CHA in the International Zeolite Association (IZA). is there.
  • the crystal structure of zeolite can be analyzed using an X-ray diffraction (XRD) apparatus.
  • the CHA-type zeolite is an X-ray diffraction spectrum obtained by powder X-ray analysis.
  • the ratio is preferably 3.1 or more.
  • Zeolite having an X-ray integral intensity ratio of 3.1 or higher has high crystallinity, hardly changes its structure due to heat, etc., has high NOx purification performance, and is excellent in heat resistance and durability.
  • the method for obtaining this X-ray integral intensity ratio is as described above.
  • composition ratio of the CHA-type zeolite SiO 2 / Al 2 O 3 means the molar ratio (SAR) of SiO 2 to Al 2 O 3 in the zeolite.
  • the composition ratio SiO 2 / Al 2 O 3 of the CHA-type zeolite according to the present invention is less than 15, preferably 5 to 14.9, and more preferably 10 to 14.9.
  • the CHA-type zeolite according to the present invention has a composition ratio SiO 2 / Al 2 O 3 of less than 15, the acid points of the zeolite can be made a sufficient number, and metal ions and ions can be obtained using the acid points. Since it can be exchanged and can carry a large amount of Cu, it is excellent in NOx purification performance.
  • the composition ratio SiO 2 / Al 2 O 3 of the CHA-type zeolite exceeds 15, the supported amount of Cu is small and the purification rate of NOx is lowered.
  • the molar ratio of zeolite (SiO 2 / Al 2 O 3 ) can be measured using fluorescent X-ray analysis (XRF).
  • the zeolite according to the present invention it is preferable that 3.5 to 6.0% by mass of Cu is supported on the zeolite. Since 3.5 to 6.0% by mass of Cu is supported, high NOx purification performance can be obtained with a small amount of zeolite.
  • the Cu is more preferably supported by 4.0 to 5.5% by mass.
  • the Cu ion exchange method can be performed by immersing the zeolite in one aqueous solution selected from a copper acetate aqueous solution, a copper nitrate aqueous solution, a copper sulfate aqueous solution and a copper chloride aqueous solution.
  • aqueous copper acetate solution is preferred. This is because a large amount of Cu can be supported at one time.
  • copper can be supported on the zeolite by ion exchange of a copper (II) acetate aqueous solution having a copper concentration of 0.1 to 2.5 mass% at a solution temperature of room temperature to 50 ° C. and atmospheric pressure.
  • the average particle size of the CHA-type zeolite according to the present invention is preferably 0.1 to 1.0 ⁇ m, and more preferably 0.1 to 0.5 ⁇ m.
  • a honeycomb catalyst is manufactured using zeolite having such a small average particle diameter, the amount of water absorption displacement becomes small.
  • the average particle size of the CHA-type zeolite according to the present invention is 0.1 to 1.0 ⁇ m, the pore size becomes an appropriate size when used as a honeycomb catalyst, and sufficient NOx purification performance can be exhibited. The amount does not increase, and the occurrence of cracks in the honeycomb catalyst can be suppressed.
  • the average particle size of the zeolite was determined by taking an SEM photograph using a scanning electron microscope (SEM, manufactured by Hitachi High-Tech, S-4800), measuring the length of all diagonal lines of 10 particles, and calculating the average value. Ask from. Measurement conditions are as follows: acceleration voltage: 1 kV, emission: 10 ⁇ A, WD: 2.2 mm or less. In general, the CHA-type zeolite particles are cubic, and become a square when two-dimensionally imaged by an SEM photograph. Therefore, there are two diagonal lines of particles.
  • CHA-type zeolite is contained in an amount of 150 to 350 g / L with respect to the entire honeycomb unit.
  • the content of the CHA-type zeolite is less than 150 g / L, the NOx purification performance decreases, and when it exceeds 350 g / L, the water absorption displacement of the honeycomb unit increases and cracks occur.
  • the content is more preferably 150 to 250 g / L.
  • the method for producing a zeolite according to the present invention includes a synthesis step of synthesizing a zeolite by reacting a raw material composition comprising a Si source, an Al source, an alkali source, water, and a structure directing agent.
  • the ratio of the number of moles of water to the total number of moles of source Si and Al of source Al is 15 or more.
  • a raw material composition comprising a Si source, an Al source, an alkali source, water and a structure directing agent is prepared.
  • the Si source refers to compounds, salts and compositions that are raw materials for the silicon component of zeolite.
  • the Si source for example, colloidal silica, amorphous silica, sodium silicate, tetraethylorthosilicate, aluminosilicate gel, and the like can be used, and two or more of these may be used in combination.
  • colloidal silica is preferable in that a zeolite having a particle size of 0.1 to 0.5 ⁇ m can be obtained.
  • Al source examples include aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, alumino-silicate gel, and dry aluminum hydroxide gel. Of these, aluminum hydroxide and dry aluminum hydroxide gel are preferred.
  • a Si source and an Al source having the same molar ratio as the molar ratio of the produced zeolite (SiO 2 / Al 2 O 3 ).
  • the molar ratio (SiO 2 / Al 2 O 3 ) is preferably 5 to 30, and more preferably 10 to 15.
  • alkali source examples include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydroxide, alkali components in aluminate and silicate, alkali components in aluminosilicate gel, and the like. Two or more of these may be used in combination. Of these, potassium hydroxide, sodium hydroxide, and lithium hydroxide are preferable.
  • the ratio of the number of moles of water to the total number of moles of Si of the Si source and Al of the Al source is 15 or more.
  • the ratio of the number of moles of water to the total number of moles of Al in the Si and Al sources is more preferably 17-25.
  • the structure directing agent (hereinafter also referred to as SDA) refers to an organic molecule that defines the pore diameter and crystal structure of zeolite.
  • SDA structure directing agent
  • Structure directing agents include hydroxides, halides, carbonates, methyl carbonates, sulfates and nitrates with N, N, N-trialkyladamantanammonium as a cation; and N, N, N-trimethylbenzylammonium ions , N-alkyl-3-quinuclidinol ions, or hydroxides, halides, carbonates, methyl carbonate salts, sulfates and nitrates with N, N, N-trialkylexoaminonorbornane as a cation At least one selected from can be used.
  • N, N, N-trimethyladamantanammonium hydroxide hereinafter also referred to as TMAAOH
  • N, N, N-trimethyladamantanammonium halide N, N, N-trimethyladamantanammonium carbonate
  • TMAAOH N, N-trimethyladamantanammonium halide
  • N, N, N-trimethyladamantanammonium carbonate It is preferable to use at least one selected from the group consisting of N, N, N-trimethyladamantanammonium methyl carbonate and N, N, N-trimethyladamantanammonium sulfate, and it is more preferable to use TMAAOH.
  • zeolite seed crystals it is preferable to add zeolite seed crystals to the raw material composition.
  • the seed crystal By using the seed crystal, the crystallization speed of the zeolite is increased, the time for producing the zeolite can be shortened, and the yield is improved.
  • a zeolite seed crystal it is preferable to use a zeolite having a CHA structure.
  • the amount of zeolite seed crystals added is preferably small, but considering the reaction rate, the effect of suppressing impurities, etc., it should be 0.1 to 20% by mass with respect to the silica component contained in the raw material composition. Preferably, the content is 0.5 to 15% by mass.
  • zeolite is synthesized by reacting the prepared raw material composition, but it is preferable to synthesize zeolite by hydrothermal synthesis of the raw material composition.
  • hydrothermal synthesis it can carry out similarly to the manufacturing method of a 1st zeolite.
  • zeolite is synthesized by reacting the prepared raw material composition. Specifically, it is preferable to synthesize zeolite by hydrothermal synthesis of the raw material composition.
  • the reaction vessel used for hydrothermal synthesis is not particularly limited as long as it is used for known hydrothermal synthesis, and may be a heat and pressure resistant vessel such as an autoclave.
  • the zeolite can be crystallized by putting the raw material composition into the reaction vessel, sealing and heating.
  • the raw material mixture When synthesizing the zeolite, the raw material mixture may be in a stationary state, but is preferably in a state of being stirred and mixed.
  • the heating temperature when synthesizing the zeolite is preferably 100 to 200 ° C, more preferably 120 to 180 ° C.
  • the heating temperature is less than 100 ° C., the crystallization rate becomes slow, and the yield tends to decrease.
  • the heating temperature exceeds 200 ° C., impurities are likely to be generated.
  • the heating time for synthesizing the zeolite is preferably 10 to 200 hours. If the heating time is less than 10 hours, unreacted raw materials remain and the yield tends to decrease. On the other hand, even when the heating time exceeds 200 hours, the yield and crystallinity are hardly improved.
  • the pressure at the time of synthesizing the zeolite is not particularly limited, and the pressure generated when the raw material composition placed in the closed container is heated to the above temperature range is sufficient, but if necessary, inert gas such as nitrogen gas can be used. Gas may be added to increase the pressure.
  • the method for producing zeolite according to the present invention after synthesizing the zeolite, it is preferably allowed to cool sufficiently, separated into solid and liquid, washed with a sufficient amount of water, and dried.
  • the drying temperature is not particularly limited, and may be any temperature from 100 to 150 ° C.
  • the synthesized zeolite contains SDA in the pores, it may be removed if necessary.
  • SDA can be removed by a liquid phase treatment using an acidic solution or a chemical solution containing an SDA decomposition component, an exchange treatment using a resin, a thermal decomposition treatment, or the like.
  • a zeolite having a CHA structure, a composition ratio SiO 2 / Al 2 O 3 of less than 15, and an average particle diameter of 0.1 to 0.5 ⁇ m can be produced.
  • the honeycomb unit may contain zeolite other than CHA-type zeolite and silicoaluminophosphate (SAPO) within a range not impairing the effects of the present invention.
  • SAPO silicoaluminophosphate
  • examples of the oxide having a positive linear expansion coefficient include particles of alumina, titania, zirconia, silica, ceria, magnesia, and the like. Two or more of these may be used in combination.
  • the inorganic particles are preferably one or more particles selected from the group consisting of alumina, titania and zirconia, and more preferably any one of alumina, titania and zirconia.
  • Having a positive coefficient of linear expansion refers to a substance whose volume of an object expands due to an increase in temperature.
  • the coefficient of linear expansion is a push-rod dilatometer whose linear expansion coefficient is known. Measurement is performed at a temperature increase rate of 10 ° C./min between 50 and 700 ° C. using alumina as a reference substance.
  • the average particle diameter of the oxide is preferably 0.01 to 5 ⁇ m, and more preferably 0.02 to 2 ⁇ m.
  • the average particle diameter of the oxide is 0.01 to 5 ⁇ m, the pore diameter of the honeycomb unit can be adjusted.
  • the average particle size of the oxide is the particle size (Dv50) at an integrated value of 50% in the particle size distribution (volume basis) obtained by the laser diffraction / scattering method.
  • the ratio (X: Y) of the volume (X) of zeolite and the volume (Y) of oxide in the honeycomb unit is 50:50 to 90:10, and 60:40 to 85 : 15 is preferable.
  • the volume ratio of the zeolite is less than 50 (when the volume ratio of the oxide exceeds 50), the NOx purification performance decreases, and when the volume ratio of the zeolite exceeds 90 (the volume ratio of the oxide is less than 10) And)
  • the effect of lowering the absolute value of the linear expansion coefficient of the honeycomb unit cannot be obtained, and the honeycomb unit is easily damaged by thermal stress.
  • the ratio (B / A) of the average particle diameter (A) of the zeolite to the average particle diameter (B) of the oxide is preferably 1/10 to 5.
  • the oxides are not buried in the gaps between the zeolites, and the NOx purification performance can be prevented from being lowered. Further, the particles can be in proper contact with each other, sufficient strength can be obtained, and cracking can be prevented.
  • the honeycomb catalyst of the present invention may contain inorganic particles other than the zeolite and the oxide as long as the effects of the present invention are not impaired.
  • examples of such inorganic particles include silicon carbide, silicon nitride, and aluminum titanate.
  • the inorganic binder contained in the honeycomb unit is not particularly limited, but is contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc. from the viewpoint of maintaining strength as a honeycomb catalyst.
  • the solid content is suitable, and two or more kinds may be used in combination.
  • the content of the inorganic binder in the honeycomb unit is preferably 3 to 20% by volume, and more preferably 5 to 15% by volume.
  • excellent NOx purification performance can be maintained without reducing the strength of the honeycomb unit.
  • the honeycomb unit preferably further contains inorganic fibers in order to improve the strength.
  • the inorganic fibers contained in the honeycomb unit are preferably made of one or more selected from the group consisting of alumina, silica, silicon carbide, silica alumina, glass, potassium titanate and aluminum borate. This is because all of them have high heat resistance, and even when used as a catalyst carrier in an SCR system, there is no melting damage and the effect as a reinforcing material can be maintained.
  • the content of inorganic fibers in the honeycomb unit is preferably 3 to 30% by volume, and more preferably 5 to 20% by volume.
  • the content is 3 to 30% by volume, it is possible to improve the strength of the honeycomb unit, to make the content of zeolite in the honeycomb unit sufficient, and to prevent the NOx purification performance from being lowered.
  • the honeycomb catalyst of the present invention is a honeycomb catalyst including a honeycomb unit that is composed of the above components and in which a plurality of through holes are arranged in parallel in the longitudinal direction with partition walls therebetween.
  • FIG. 1 shows an example of the honeycomb catalyst of the present invention.
  • a honeycomb catalyst 10 shown in FIG. 1 includes a single honeycomb unit 11 in which a plurality of through-holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b therebetween, and an outer peripheral coating layer 12 is provided on the outer peripheral surface of the honeycomb unit 11. Is formed.
  • the honeycomb unit 11 contains zeolite and an inorganic binder.
  • the maximum peak pore diameter of the partition walls of the honeycomb unit (hereinafter sometimes referred to as the maximum peak pore diameter of the honeycomb unit) is preferably 0.03 to 0.20 ⁇ m. More preferably, it is from 05 to 0.15 ⁇ m.
  • the pore size of the honeycomb unit can be measured using a mercury intrusion method.
  • the mercury contact angle is 130 °
  • the surface tension is 485 mN / m
  • the pore diameter is in the range of 0.01 to 100 ⁇ m.
  • the value of the pore diameter at the maximum peak in this range is called the maximum peak pore diameter.
  • the porosity of the honeycomb unit is preferably 40 to 70%.
  • the porosity of the honeycomb unit is less than 40%, the exhaust gas hardly enters the partition walls of the honeycomb unit, and the zeolite is not effectively used for the purification of NOx.
  • the porosity of the honeycomb unit exceeds 70%, the strength of the honeycomb unit becomes insufficient.
  • the porosity of the honeycomb unit can be measured by a gravimetric method.
  • the method for measuring the porosity by the gravimetric method is as follows.
  • the honeycomb unit is cut into a size of 7 cells ⁇ 7 cells ⁇ 10 mm to obtain a measurement sample.
  • This sample is ultrasonically cleaned with ion-exchanged water and acetone, and then dried in an oven at 100 ° C.
  • the dimensions of the cross-sectional shape of the sample are measured using a measuring microscope (Mekoning® Microscope manufactured by Nikon, 100 ⁇ magnification), and the volume is obtained from geometric calculation.
  • the volume is calculated by image processing of a cross-sectional photograph.
  • the weight when the sample is assumed to be a complete dense body is calculated.
  • the measurement procedure with the pycnometer is as follows.
  • the honeycomb unit is pulverized to prepare 23.6 cc of powder, and the obtained powder is dried at 200 ° C. for 8 hours. Thereafter, the true density is measured according to JIS-R-1620 (1995) using an Auto Pycnometer 1320 (manufactured by Micromeritics). The exhaust time at this time is 40 min.
  • the actual weight of the sample is measured with an electronic balance (HR202i manufactured by Shimadzu Corporation), and the porosity is calculated by the following calculation formula. 100- (actual weight / weight as dense body) ⁇ 100 (%)
  • the opening ratio of the cross section perpendicular to the longitudinal direction of the honeycomb unit is preferably 50 to 75%. If the opening ratio of the cross section perpendicular to the longitudinal direction of the honeycomb unit is less than 50%, zeolite is not effectively used for NOx purification. On the other hand, when the opening ratio of the cross section perpendicular to the longitudinal direction of the honeycomb unit exceeds 75%, the strength of the honeycomb unit becomes insufficient.
  • the density of through-holes in a cross section perpendicular to the longitudinal direction of the honeycomb unit is preferably 62 to 186 holes / cm 2 .
  • the density of the through-holes is 62 to 186 / cm 2 , the zeolite and the exhaust gas can easily come into contact with each other, and the NOx purification performance can be sufficiently exerted, and an increase in the pressure loss of the honeycomb catalyst is suppressed. Can do.
  • the thickness of the partition walls of the honeycomb unit is preferably 0.1 to 0.3 mm, and more preferably 0.1 to 0.25 mm.
  • the thickness of the partition wall of the honeycomb unit is 0.1 to 0.3 mm, sufficient strength can be obtained, and exhaust gas can easily enter the inside of the partition wall of the honeycomb unit, so that zeolite is effectively used for NOx purification.
  • the thickness of the outer peripheral coat layer is preferably 0.1 to 5.0 mm.
  • the thickness of the outer peripheral coat layer is less than 0.1 mm, the effect of improving the strength of the honeycomb catalyst becomes insufficient.
  • the thickness of the outer peripheral coat layer exceeds 5.0 mm, the content of zeolite per unit volume of the honeycomb catalyst decreases, and the NOx purification performance decreases.
  • the shape of the honeycomb catalyst of the present invention is not limited to a cylindrical shape, and examples thereof include a prismatic shape, an elliptical cylindrical shape, a long cylindrical shape, and a rounded chamfered prismatic shape (for example, a rounded chamfered triangular prism shape).
  • the diameter is 140 to 350 mm and the length is 75 to 310 mm.
  • the shape of the through hole is not limited to a quadrangular prism shape, and examples thereof include a triangular prism shape and a hexagonal prism shape.
  • the above honeycomb catalyst of the present invention can be manufactured, for example, as follows. First, it includes a zeolite and an inorganic binder, and if necessary, is extruded using a raw material paste further containing inorganic fibers and inorganic particles, and a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween. A columnar honeycomb formed body is produced.
  • the inorganic binder contained in the raw material paste is as described above, and an organic binder, a dispersion medium, a molding aid and the like may be appropriately added to the raw material paste as necessary.
  • the organic binder is not particularly limited, and examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, phenol resin, and epoxy resin, and two or more kinds may be used in combination.
  • the addition amount of the organic binder is preferably 1 to 10% with respect to the total mass of zeolite, inorganic particles, inorganic binder, and inorganic fibers.
  • the dispersion medium is not particularly limited, and examples thereof include water, organic solvents such as benzene, alcohols such as methanol, and the like.
  • the molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like, and two or more kinds may be used in combination.
  • a pore former may be added to the raw material paste as necessary. Although it does not specifically limit as a pore making material, A polystyrene particle, an acrylic particle, starch, etc. are mentioned, You may use 2 or more types together. Of these, polystyrene particles are preferred.
  • the pore size distribution of the partition walls can be controlled within a predetermined range.
  • the pore size distribution of the partition walls can be controlled within a predetermined range by controlling the particle size of the inorganic particles.
  • the raw material paste When preparing the raw material paste, it is desirable to mix and knead, and it may be mixed using a mixer, an attritor or the like, or may be kneaded using a kneader or the like.
  • the honeycomb formed body is dried by using a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, a freeze dryer or the like to prepare a honeycomb dried body.
  • a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, a freeze dryer or the like to prepare a honeycomb dried body.
  • honeycomb dried body is degreased to produce a honeycomb degreased body.
  • the degreasing conditions can be appropriately selected depending on the type and amount of the organic substance contained in the dried honeycomb body, but is preferably 200 to 500 ° C. for 2 to 6 hours.
  • the honeycomb degreased body is fired to produce a cylindrical honeycomb unit.
  • the firing temperature is preferably 600 to 1000 ° C., more preferably 600 to 800 ° C.
  • the firing temperature is 600 to 1000 ° C.
  • a honeycomb unit having sufficient strength can be obtained without reducing the reaction sites of zeolite.
  • the outer peripheral coat layer paste is applied to the outer peripheral surface excluding both end surfaces of the cylindrical honeycomb unit.
  • a paste for outer periphery coating layers The mixture of an inorganic binder and an inorganic particle, the mixture of an inorganic binder and an inorganic fiber, the mixture of an inorganic binder, an inorganic particle, and an inorganic fiber etc. are mentioned.
  • the inorganic binder contained in the outer periphery coating layer paste is not particularly limited, but is added as silica sol, alumina sol or the like, and two or more kinds may be used in combination. Among these, it is preferable to add as silica sol.
  • the inorganic particles contained in the outer coat layer paste are not particularly limited, but oxide particles such as zeolite, eucryptite, alumina and silica, carbide particles such as silicon carbide, and nitride particles such as silicon nitride and boron nitride. Etc., and two or more of them may be used in combination. Among them, eucryptite particles having a linear expansion coefficient close to that of the honeycomb unit are preferable.
  • the inorganic fiber contained in the outer periphery coat layer paste is not particularly limited, and examples thereof include silica alumina fiber, mullite fiber, alumina fiber, silica fiber, and glass fiber, and two or more kinds may be used in combination. Among these, glass fiber is preferable.
  • the outer periphery coating layer paste may further contain an organic binder.
  • the outer periphery coat layer paste may further contain balloons, pore formers, and the like, which are fine hollow spheres of oxide ceramics.
  • the balloon contained in the outer periphery coating layer paste is not particularly limited, and examples thereof include alumina balloons, glass micro balloons, shirasu balloons, fly ash balloons, mullite balloons, and the like, and two or more kinds may be used in combination. Among these, an alumina balloon is preferable.
  • the pore former contained in the outer periphery coat layer paste is not particularly limited, and examples thereof include spherical acrylic particles and graphite, and two or more kinds may be used in combination.
  • the honeycomb unit 11 coated with the outer periphery coating layer paste is dried and solidified to produce a cylindrical honeycomb catalyst.
  • the outer peripheral coat layer paste contains an organic binder, it is preferably degreased.
  • the degreasing conditions can be appropriately selected depending on the kind and amount of the organic substance, but it is preferably 1 hour at 500 ° C.
  • FIG. 2 shows another example of the honeycomb catalyst of the present invention.
  • a honeycomb catalyst 10 ′ shown in FIG. 2 has a plurality of honeycomb units 11 ′ (see FIG. 3) in which a plurality of through-holes 11 a are arranged in parallel in the longitudinal direction with partition walls 11 b interposed therebetween. Except for this, the configuration is the same as that of the honeycomb catalyst 10.
  • the cross-sectional area of the cross section perpendicular to the longitudinal direction of the honeycomb unit 11 ′ is preferably 10 to 200 cm 2 .
  • the cross-sectional area is less than 10 cm 2 , the pressure loss of the honeycomb catalyst 10 ′ increases.
  • the cross-sectional area exceeds 200 cm 2 , it is difficult to bond the honeycomb units 11 ′.
  • the honeycomb unit 11 ′ has the same configuration as the honeycomb unit 11 except for the cross-sectional area of the cross section perpendicular to the longitudinal direction.
  • the thickness of the adhesive layer 13 is preferably 0.1 to 3.0 mm. When the thickness of the adhesive layer 13 is less than 0.1 mm, the adhesive strength of the honeycomb unit 11 ′ becomes insufficient. On the other hand, when the thickness of the adhesive layer 13 exceeds 3.0 mm, the pressure loss of the honeycomb catalyst 10 ′ increases or cracks occur in the adhesive layer.
  • a fan-shaped honeycomb unit 11 ′ is manufactured in the same manner as the honeycomb unit 11 constituting the honeycomb catalyst 10.
  • an adhesive layer paste is applied to the outer peripheral surface excluding the arc side of the honeycomb unit 11 ′, the honeycomb unit 11 ′ is adhered, and dried and solidified to produce an aggregate of the honeycomb units 11 ′.
  • the adhesive layer paste is not particularly limited, and examples thereof include a mixture of inorganic binder and inorganic particles, a mixture of inorganic binder and inorganic fibers, a mixture of inorganic binder, inorganic particles, and inorganic fibers.
  • the inorganic binder contained in the adhesive layer paste is not particularly limited, but is added as silica sol, alumina sol or the like, and two or more kinds may be used in combination. Among these, it is preferable to add as silica sol.
  • the inorganic particles contained in the adhesive layer paste are not particularly limited, but oxide particles such as zeolite, eucryptite, alumina and silica, carbide particles such as silicon carbide, nitride particles such as silicon nitride and boron nitride, etc. And two or more of them may be used in combination. Among them, eucryptite particles having a thermal expansion coefficient close to that of the honeycomb unit are preferable.
  • the inorganic fiber contained in the adhesive layer paste is not particularly limited, and examples thereof include silica alumina fiber, mullite fiber, alumina fiber, silica fiber and the like, and two or more kinds may be used in combination. Among these, alumina fibers are preferable.
  • the adhesive layer paste may contain an organic binder.
  • the organic binder contained in the adhesive layer paste is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like, and two or more kinds may be used in combination.
  • the adhesive layer paste may further include balloons, pore formers, and the like, which are fine hollow spheres of oxide ceramics.
  • the balloon contained in the adhesive layer paste is not particularly limited, and examples thereof include an alumina balloon, a glass microballoon, a shirasu balloon, a fly ash balloon, and a mullite balloon, and two or more kinds may be used in combination. Among these, an alumina balloon is preferable.
  • the pore former contained in the adhesive layer paste is not particularly limited, and examples thereof include spherical acrylic particles and graphite, and two or more kinds may be used in combination.
  • the aggregate of the honeycomb units 11 ′ is cut and polished as necessary to produce the aggregate of the cylindrical honeycomb units 11 ′.
  • the outer peripheral coat layer paste is applied to the outer peripheral surface excluding both end surfaces of the aggregate of the cylindrical honeycomb unit 11 ′.
  • the outer periphery coat layer paste may be the same as or different from the adhesive layer paste.
  • a columnar honeycomb catalyst 10 ′ is manufactured by drying and solidifying the aggregate of columnar honeycomb units 11 ′ coated with the outer periphery coating layer paste.
  • an organic binder is contained in the adhesive layer paste and / or the outer peripheral coat layer paste, it is preferable to degrease.
  • the degreasing conditions can be appropriately selected depending on the kind and amount of the organic substance, but it is preferably 1 hour at 500 ° C.
  • the honeycomb catalyst 10 ′ is configured by bonding four honeycomb units 11 ′ via the adhesive layer 13, but the number of honeycomb units constituting the honeycomb catalyst is not particularly limited.
  • a columnar honeycomb catalyst may be configured by adhering 16 square columnar honeycomb units via an adhesive layer.
  • honeycomb catalyst 10 and 10 ′ may not have the outer peripheral coat layer 12 formed thereon.
  • Example 1 (Preparation of honeycomb catalyst) Glass fiber having 22.7% by mass of CHA-type zeolite shown in Table 1, 20.2% by mass of titanium oxide having an average particle size of 0.2 ⁇ m, 6.8% by mass of pseudoboehmite as an inorganic binder, and an average fiber length of 100 ⁇ m 6.8% by mass of methyl cellulose, 6.2% by mass of methyl cellulose, 3.4% by mass of surfactant, 4.8% by mass of polystyrene particles having an average particle diameter of 0.8 ⁇ m as pore former and ion-exchanged water.
  • a raw material paste was prepared by mixing and kneading 29.2% by mass.
  • the zeolite used after the copper ion exchange was prepared by mixing and kneading 29.2% by mass.
  • the raw material paste was extruded using an extrusion molding machine to produce a honeycomb formed body. Then, using a vacuum microwave dryer, the honeycomb formed body was dried at an output of 4.5 kW and a reduced pressure of 6.7 kPa for 7 minutes, and then degreased and fired at an oxygen concentration of 1% and 700 ° C. for 5 hours. Unit).
  • the honeycomb unit had a regular quadrangular prism shape with a side of 35 mm and a length of 150 mm, a through hole density of 124 holes / cm 2 , and a partition wall thickness of 0.20 mm.
  • Example 2 Glass fiber having 18.0% by mass of CHA-type zeolite shown in Table 1, 32.8% by mass of titanium oxide having an average particle diameter of 0.2 ⁇ m, 6.6% by mass of pseudoboehmite as an inorganic binder, and an average fiber length of 100 ⁇ m. 6.6% by mass, 5.5% by mass of methylcellulose, 3.0% by mass of surfactant, 3.8% by mass of polystyrene particles having an average particle diameter of 0.8 ⁇ m as pore former and ion-exchanged water.
  • a raw material paste was prepared by mixing and kneading 23.8% by mass. The zeolite was used without exchanging copper ions. Next, using the prepared raw material paste, a honeycomb catalyst of Example 2 was produced in the same manner as Example 1.
  • Example 3 Glass fiber having 31.2% by mass of CHA-type zeolite shown in Table 1, 6.3% by mass of titanium oxide having an average particle diameter of 0.2 ⁇ m, 6.4% by mass of pseudoboehmite as an inorganic binder, and an average fiber length of 100 ⁇ m 6.4% by mass, methylcellulose 6.7% by mass, surfactant 3.7% by mass, polystyrene particles having an average particle size of 0.8 ⁇ m as pore former, 6.6% by mass and ion-exchanged water.
  • a raw material paste was prepared by mixing and kneading 32.7% by mass. The zeolite was used without exchanging copper ions.
  • a honeycomb catalyst of Example 3 was produced in the same manner as Example 1 using the prepared raw material paste.
  • Example 4 A glass fiber having 22.2% by mass of CHA-type zeolite shown in Table 1, 24.8% by mass of zirconia having an average particle size of 0.04 ⁇ m, 5.8% by mass of pseudoboehmite as an inorganic binder, and an average fiber length of 100 ⁇ m.
  • a raw material paste was prepared by mixing and kneading 5.8 mass%, methyl cellulose 6.2 mass%, surfactant 3.4 mass%, and ion-exchanged water 31.7 mass%.
  • the zeolite used after the copper ion exchange was produced in the same manner as Example 1 using the prepared raw material paste.
  • Example 5 The CHA-type zeolite shown in Table 1 is 28.3% by mass, the alumina having an average particle diameter of 2.6 ⁇ m is 12.2% by mass, the pseudoboehmite is 6.5% by mass as an inorganic binder, and the glass fiber has an average fiber length of 100 ⁇ m. 6.5% by mass, 6.4% by mass of methylcellulose, 3.5% by mass of surfactant, 5.9% by mass of polystyrene particles having an average particle diameter of 0.8 ⁇ m as a pore former and 30 of ion-exchanged water A material paste was prepared by mixing and kneading 5% by mass. In addition, the zeolite used after the copper ion exchange. Next, a honeycomb catalyst of Example 5 was produced in the same manner as Example 1 using the prepared raw material paste.
  • Example 6 A glass fiber having 22.2% by mass of CHA-type zeolite shown in Table 1, 24.8% by mass of zirconia having an average particle size of 0.04 ⁇ m, 5.8% by mass of pseudoboehmite as an inorganic binder, and an average fiber length of 100 ⁇ m.
  • a raw material paste was prepared by mixing and kneading 5.8 mass%, methylcellulose 6.2 mass%, surfactant 3.4 mass%, and ion-exchanged water 31.7 mass%.
  • the zeolite used after the copper ion exchange was produced in the same manner as Example 1 using the prepared raw material paste.
  • Example 1 40.0% by mass of the CHA-type zeolite shown in Table 1, 7.4% by mass of pseudoboehmite as an inorganic binder, 7.3% by mass of glass fiber having an average fiber length of 100 ⁇ m, 6.7% by mass of methylcellulose, interface
  • a raw material paste was prepared by mixing and kneading 3.6% by mass of the activator and 35.0% by mass of ion-exchanged water.
  • the zeolite used after the copper ion exchange was produced in the same manner as Example 1 using the prepared raw material paste.
  • Comparative Example 2 Glass fiber with 25.4% by mass of CHA-type zeolite shown in Table 1, 19.9% by mass of titanium oxide having an average particle size of 0.2 ⁇ m, 6.7% by mass of pseudoboehmite as an inorganic binder, and an average fiber length of 100 ⁇ m 6.7% by weight of methyl cellulose, 6.0% by weight of methyl cellulose, 3.3% by weight of surfactant, 5.3% by weight of polystyrene particles having an average particle diameter of 0.8 ⁇ m as pore former and ion-exchanged water.
  • a raw material paste was prepared by mixing and kneading 26.7% by mass. The zeolite was used without exchanging copper ions.
  • a honeycomb catalyst of Comparative Example 2 was produced in the same manner as Example 1 using the prepared raw material paste.
  • a measurement sample of 5 mm ⁇ 5 mm ⁇ 25 mm was cut out from each honeycomb unit using a diamond cutter. Thereafter, the sample was dried at 200 ° C. for 2 hours, the weight was measured, and the sample was allowed to stand in a steam atmosphere until the water absorption rate of the measurement sample reached 10%.
  • each detection rod is installed so as to be in contact with the central portion of the upper surface (that is, the upper region of 5 mm ⁇ 25 mm).
  • the measurement sample and the reference sample are held from room temperature at 50 ° C. for 10 hours, then heated to 700 ° C. at a rate of 10 ° C./min, and cooled to room temperature at 10 ° C./min. It was.
  • the measurement was performed in an atmosphere with a He flow rate of 100 ml / min.
  • the measurement sample and the reference sample are thermally expanded, and the measurement sample is displaced by water absorption. This amount of change is detected by the detection rod. Therefore, the linear expansion coefficient of the measurement sample (honeycomb unit) is obtained from the difference in change between the reference sample and the measurement sample.
  • thermal expansion coefficient measuring device manufactured by BRUKER, NETZSCH DIL402C was used.
  • the NOx purification rate [%] was calculated while flowing a simulated gas at 525 ° C. at SV: 150,000 / hr.
  • the constituent components of the simulated gas at this time were 315 ppm nitric oxide, 35 ppm nitrogen dioxide, 385 ppm ammonia, 10% oxygen, 5% carbon dioxide, 5% water, and nitrogen.
  • Table 1 shows the NOx purification rates of the honeycomb catalysts using the zeolites obtained in Examples 1 to 6 and Comparative Examples 1 and 2.
  • test piece was immersed in water for 1 hr, water on the sample surface was removed by air blow, and the distance between the outermost walls during water absorption was measured by the same measurement method.
  • the water absorption displacement is given by equation (2) (Distance between outermost walls when absolutely dry-Distance between outermost walls when absorbing water) / (Distance between outermost walls when absolutely dry) x 100 (1)
  • Table 1 shows the water absorption displacement of the honeycomb catalysts using the zeolites obtained in Examples 1 to 6 and Comparative Examples 1 and 2 calculated in (1).
  • the linear expansion coefficient is within ⁇ 4 ⁇ 10 ⁇ 6 , there is no risk of cracking during use, and both the NOx purification rate and the water absorption displacement are observed. Good results were obtained.
  • the honeycomb catalyst of Comparative Example 1 had a high linear expansion coefficient of 4.2 ⁇ 10 ⁇ 6 .
  • the honeycomb catalyst of Comparative Example 2 had a low NOx purification performance.

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